Patent GB-702602-A (GB)
Title: New acylated aromatic tri-fluoromethyl-aryl-amino-sulphonic acids and processes for their preparation
IPC: C07G99/00
Filed: 1951-04-19
Abstract: The invention comprises (1) acylated aminosulphonic acids of the formula Z-NH-CO-R, Z-NH-SO2-R or Z-NH-CO-NH-R, Z being a sulphonated aromatic radical and R an aliphatic, araliphatic or aromatic radical, characterized by the presence of a trifluoromethyl group in at least one aromatic nucleus and by the presence in Z and/or R of a diphenyl, diphenylether, diphenylsulphide, diphenylsulphoxide, diphenylsulphone, diphenylmethane, diphenylurea or stilbene residue; and (2) the preparation of the above compounds and similar compounds where Z is heterocyclic or the acyl group is replaced by a triazine ring, followed if desired by sulphonation or halogenation.  The preparation is effected by treating Z-NH2 with reactive derivatives of carboxylic acids (mono and poly), sulphonic acids, carbonic or cyanuric acids.  Suitable derivatives are carboxylic and sulphonic acid halides, esters and anhydrides, carbonic halides, esters and amides, isocyanates, carboxylic azides, N-halo-carboxylic acid amides, and cyanuric halides, halo-amides and thio derivatives.  When using carbonic acid derivatives the residues R and Z may be introduced separately.  When using cyanuric compounds the third atom or group may remain or be reacted with a substance containing an amino, hydroxy or thio group.  When using these and similar bifunctional agents the groups Z and R may be the same or different. The products are free from groups imparting colour.  In the examples the following are condensed together: (1) 4-methyl-41-trifluoromethyl-21-amino-diphenylether-2 -sulphonic acid and palm kernel oil fatty acid chloride (mainly lauric); (2) 4 - chloro - 41 - trifluoromethyl - 21 - amino - diphenylether - 2 - sulphonic acid and 3:4 - dichlorobenzoyl chloride; (3) 4 - amino - 41 - methyl - diphenylether - 2 - sulphonic acid and 3 - trifluoromethyl - benzoyl chloride; (4) amino of (2) and p-chlorophenylacetyl chloride; (5) amine of (2) and succinic dichloride; (6) as in (1) using the 5-methyl isomer; the product is chlorinated; (7) 3:4-dichloraniline-6-sulphonic acid and 3-trifluoromethyl-diphenylether - 41 - carboxylic chloride; (8) 3-trifluoromethyl - aniline - 6 - sulphonic acid and 4 - chloro - diphenylether - 41 - carboxylic chloride; (9) as in (8) using the 41 - sulphonyl chloride; (10) amine of (2) and 3-trifluoromethyl - 4 - chlorobenzene - sulphonyl chloride; (11) amine of (1) and phosgene; (12) 4-amino-41-chloro-diphenylether and 3-trifluoromethyl - phenyl isocyanate, the product being sulphonated; (13) 4 - n - amyl - 41 - amino - diphenylether - 21 - sulphonic acid and 3-trifluoromethyl-phenyl-carbamyl chloride; (14) amine of (2) and 3:4-dichlorophenyl isocyanate; (15) 3:4-dimethyl-aniline-6-sulphonic acid and 3-trifluoromethyl-6-(41-t-amylphenoxy) - phenyl - carbamyl chloride; (16) 3-trifluoromethyl-4-chloraniline and 2-(21-sulpho - 41 - chlorophenoxy) - 5 - chlor - phenyl - carbamic acid phenyl ester; (17) amine of (2) and 3:4-dichlorobenzoyl azide; (18) amine of (2) and p-chlorobenzoic acid chloramide; (19) 4-chloro-4-trifluoromethyl-21-amino-diphenylether and 3:4-dichlorophenyl isocyanate, the product being sulphonated; (20) 2 - amino - 4:41 - dichloro - diphenylether - 21 - sulphonic acid and 3-trifluoromethyl - 6 - (p - chlorophenoxy) - phenyl isocyanate; (21) 2 - amino - 41 - chloro - 4 - trifluoromethyl - diphenylether - 21 - sulphonic acid and isocyanate of (20); (22) amine of (1) and 3-trifluoromethyl - 6 - (p - tolyloxy) - phenyl isocyanate; (23) 2 - amino - 4 - trifluoro - methyl - 41; 51 - dichloro - diphenylether - 21 - sulphonic acid and 3 - trifluoromethyl - 6 - (31:41 - dichlorophenoxy) - phenyl isocyanate; (24) amine of (21) and 3-chloro-4-(p-chlorophenoxy) - phenyl isocyanate; (25) 4-amino - 41 - chloro - diphenylether - 2 - sulphonic acid and isocyanate of (20); (26) 4-amino-31:41-dichloro-diphenylsulphide-2-sulphonic acid and isocyanate of (23); (27) amine of (21) and diphenylether - 4 - isocyanate, the product being chlorinated; (28) 2-amino-4-trifluoromethyl - 41 - chloro - diphenylether and 4:41 - dichloro - diphenylether - 2 - sulphonic acid - 21 - carbamic acid phenyl ester; (29) 3-trifluoromethyl - 4 - chloraniline - 6 - sulphonic acid and isocyanate of (24); (30) amine of (29) and 2 - (p - chlorophenoxy) - 5 - trifluoro - methyl - phenyl isocyanate; (31) amine of (28) and 3:4-dichloro-6-sulphophenyl carbamic acid phenyl ester; (32) 3:4-dichloraniline-6-sulphonic acid and 3-methyl-41-trifluoromethyl-diphenylether - 21 - isocyanate, the product being chlorinated; (33) amine of (29) and 3:4 - dichloro - diphenylsulphide-41-isocyanate; (34) cyanuric chloride, 2 mols. of amine of (2) and 1 mol. of methanol; (35) cyanuric chloride, 2 mols. of 4-amino-31-methyl-diphenylether-2-sulphonic acid and 1 mol. of 3-trifluoromethylaniline; the product is chlorinated by treatment with sodium chlorate and hydrochloric acid; (36) amine of (7) and 2:41-dichloro - 31 - trifluoromethyl - diphenylurea - 5 - isocyanate. Many other reactants and products are mentioned.  Amino - diphenylethers used as starting materials are made by condensing the appropriate phenols with substituted chlorobenzenes (one of the reactants containing a nitro group), sulphonating if necessary and finally reducing the nitro group. Thus are prepared 2-amino-4-trifluoromethyl-41-methyl-, 2-amino - 4 - trifluoromethyl - 41 - chloro - and 2 - amino - 4 - trifluoromethyl - 51 - methyl - diphenyl - ether - 21 - sulphonic acids and 2 - amino - 4 - trifluoromethyl - 41 - chloro - diphenylether.  The first of these and 2-amino - 4 - trifluoromethyl - 41:51 - dichloro - diphenylether - 21 - sulphonic acid are also prepared by sulphonating the amino compounds.  Many other products are mentioned.  Carbonic derivatives of amines, e.g. urethanes, carbamyl chlorides and isocyanates are made from the amines by treatment with the appropriate carbonic acid derivative.  The preparation is described of 3-trifluoromethyl-6-(41 - t - amylphenoxy) - phenyl - carbamic chloride, 3 - trifluoromethyl - 6 -(p - chloro - phenoxy) - phenyl isocyanate and 3:4 - dichloro - diphenylsulphide - 41 - isocyanate.  Many amines are specified as starting materials.  3 - Trifluoromethyl - diphenylether - 41 - carboxylic acid chloride is prepared from 3-trifluoromethyl - 41 - amino - diphenylether by diazotization, conversion to 41-cyano compound, hydrolysis to free acid and treatment with thionyl chloride.  4-Chlorobenzoic acid N-chloramide is made by chlorinating 4-chlorobenzamide.